Dyestuffs of the dioxazine series and a process of preparing them



Patented Sept. 13, 1938 Georg Kranzlein and Heinrich Greune,Frankforton-the-Main, and Gerhard Langbein, Hoiheimin-Taunus, Germany,assignors to General Aniline Works, Inc., New York, N. Y., a corporationof Delaware No Drawing. Application February 11, 1935, Se-

rial No. 6,096, In Germany February 15, 1934 4 Claims. (Cl. 260152) Thisinvention relates to dyestufis of the dioxazine series, moreparticularly to those which contain radicals of azo-dyestufis, and aprocess of preparing them.

pyrene, aminochrysene or the like are combined as diazo components onaromatic amines; furthermore derivatives or substitution products ofsuch amino-azo-dyestufis or amino-disand 5 We have found that by heatingat a temperapoly-azo-dyestuffs or the sulfonic acids of all 5 ture aboveabout 150 C. a compound of the genthe dyestufis mentioned. eral formula:In view of the large number of available parent X materials, the shadesof the final dyestuffs obtained may be varied within wide limits andtheir 0 T /0 substantive character and fastness properties may beinfluenced. The dioxazine dyestuffs obtainable by heating 0 NHR thediaryl-aminoquinones of the above general X formula in a solvent of highboiling point may wherein R means the radical of an azo-dyestufi 3 FQbtamed g Pi ope-lauon 3 L4- 15 bound at an aromatic carbon atom and Xmeans enzfqumones an e ammOJaZOT yes u by hydrogen halogen or alkyl inthe presence of a heating them above about 150 C. 1n solvents of highboiling point, if required with addition of solvent of high bo1l1ngpoint, with or w1thout or anic OX1 dizin a ems met 1 addition of anorganic or inorganic oxidizing orgalfilc or m g g g agent a metalchloride or an acylating agent or chlo'ndes or acylatmg agents 20 It isalso possible in some cases to obtain the w1th addition of two or moreof these substances, dioxazined yestuiis from the d1arylam1noqu1nonesnew mtensely colored products are obtainable which may be considered asdioxazine dyestuffs by t-reatmg t-hemlwlth strong Sulfuric acld orcontaining azo-groups and which correspond to fuming Sulfuric-81cmadvantageously in the presthe 0110 wing general formula, ence of anox1d1zing agent in which case the 25 water-soluble sulfonic acids maydirectly be ob- X tained. Diarylaminoquinone-derivatives con- N\ 0taining sulio-groups may also be transformed in this manner into thedioxazine-dyestuifs.

R R The following examples serve to illustrate the 30 invention, butthey are not intended to limit it thereto, the parts being by weight:

X (1) 10 parts of the intermediate product obwherein R represents theradical of an azo-dyetainable by condensation of para-amino-azobenstufibound at an aromatic carbon atomand X zene and toluquinone in alcoholare heated to 5 means hydrogen, halogen or alkyl. boilingfor 2 hours in100 parts of nitrobenzene In a finely dispersed state, they may be usedwith'addition of 5 parts of meta-nitrobenzenesulin the usual manner aspigment dyes, for infochloride. The whole is filtered by suction atstance, for coloring caoutchouc; when sulionated 130 C(and the solidmatter is washed with nitro- 40 they represent valuable water-solubledyestufis benzene and alcohol. The dyestuff which is ob- 40 for thevegetable, animal or artificial fiber, for 'tained in the form of smallleaflets having a instance, viscose artificial silk, or mixed fabrics.green surface luster dissolves in sulfuric acid The newdyestufi-sulfonic acids are distinguished monohydrate to a yellow-greensolution and in a by their affinity for the vegetable fiber and finelydivided state forms a violet pigment.

their good fastness properties. In the form of The pigment may besulfonated in fuming sul- 45 their barium or calcium salt or anothersuitable furic acid of 20% strength in known manner, salt they may beused as pigments. The sulfonic acid obtained dyes the animal, vege- Asaminoazo-dyestuffs suitable for the inventable and. artificial fiber(viscose artificial silk) tion there may be mentioned, for instance:violet tints.

Amino-azo-benzene, amino-azo-naphthalene, (2) 10 parts of theintermediate product ob- 50 benzene-azo-naphthy b e-a -a tainable bycondensation of 4-benzeneazo-1- thramine, benzene-azom noiph nyl-amine,naphthylamine and chloranil are heated toboilbenzene-azo-aminocarbazole, or dyestuffs in ing for half an hour inparts of nitrobenzene which, for instance, naphthylamine, anthramine,with addition of 5 parts of para-toluenesulfochlo- 55amino-diphenylamine, amino-carbazole, aminoride. The whole is filteredby suction at C. 55

and the solid matter is washed with nitrobenzene and alcohol. Thedyestuff obtained forms small needles having a grey-green surface. Itdissolves in sulfuric acid monohydrate to a redbrown solution. In afinely divided state it forms a blue pigment.

10 parts of the pigment are stirred for about 1 hour at .about 75 C. in200 parts of fuming sulfuric acid of 20% strength. The whole is pouredon ice and sodium chloride, filtered with suction and the solid matteris washed with a solution of sodium chloride until neutral. The sulfonicacid dissolves in water to a green solution and dyes the animal andvegetable fiber and.

sodium carbonate, filtered with suction and washed again with sodiumchloride solution until neutral. The dyestufi dissolves in water to areddish-blue solution and dyes the animal and vegetable fiber andviscose artificial silk blue tints. 5 It has good fastness properties.

We claim:

1. The members of the group consisting of compounds of the generalformula:

viscose artificial silk clear, green tints. The dyeings have goodfastness properties. In the form X of its barium or calcium salt thesulfonic acid wherein R represents the radical f an represents valuablegreen pigment dyes. By efd stufi' and X means a member f the groupfecting the sulfonation in fuming sulfuric acid of consisting ofhydrogen, halogen and alkyl, and strength at 45 C., a blue greensulfonic acid sulfonic a id compounds thereof, 20 is obtained. 2. Thecompound of the formula:

(3) 10 parts of the product obtainable by condensation of4-amino-1.2azonaphthalene and dichlorobenzoquinone are heated to boilingfor half an hour in 100 parts of nitrobenzene with addition of 5 partsof benzoylchloride. The

whole is filtered with suction, while hot, and the solid matter iswashed with nitrobenzene and alcohol. The dioxazine dyestuff which isobtained in the form of needles having a reddish surface dissolves inconcentrated sulfuric acid to a greyblue solution and yields ablue-violet pigment. By sulfonation in fuming sulfuric acid at 20%strength a sulfonic acid is obtained which dyes cotton and viscoseartificial silk blue-green tints.

(4) 10 parts of the intermediate product obtainable by condensation ofl-aminoazobenzene- 4'-sulfonic acid and chloranil in aqueous alcohol arestirred for about 1 hour at 150 C. in 200 parts of fuming sulfuric acidof 5% strength. After cooling, the whole is poured on ice, filtered withsuction and the solid matter is washed with sodium chloride solutionuntil neutral. In order to transform completely the sulfonic acid intothe sodium salt, it is stirred for some time with dilute sodium chloridesolution with addition of which contains sulfonic acid groups, saidcompound dissolving in water to a green solution and dyeing the animaland vegetable fiber and viscose artificial silk green tints.

3. The compound of the formula:

01 V i N\ o N=N@ o a N which contains sulfonic acid groups, saidcompound dyeing cotton blue-green tints.

which contains sulfonic acid groups, said compound dissolving in waterto a reddish-blue solution and dyeing the animal and vegetable fiber andviscose artificial silk blue tints. I

GEORG KRANZLEIN. HEINRICH GREUNE; GERHARD LANGBEIN.

